CN100342082C - Method for Improving Electrical Properties of Papermaking Compositions Using Carbon Dioxide - Google Patents
Method for Improving Electrical Properties of Papermaking Compositions Using Carbon Dioxide Download PDFInfo
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- CN100342082C CN100342082C CNB038233169A CN03823316A CN100342082C CN 100342082 C CN100342082 C CN 100342082C CN B038233169 A CNB038233169 A CN B038233169A CN 03823316 A CN03823316 A CN 03823316A CN 100342082 C CN100342082 C CN 100342082C
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- making compositions
- paper making
- paper
- carbon dioxide
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
- D21H23/06—Controlling the addition
- D21H23/08—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/65—Acid compounds
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Abstract
Carbon dioxide can be used to adjust the electrical properties of the papermaking composition. The papermaking composition may comprise a colloidal phase, an aqueous phase and optionally pulp fibers. Examples of electrical properties whose values can be adjusted include: zeta potential, charge requirement, conductivity, and flow potential. Carbon dioxide can be introduced into the papermaking process at a number of different locations, including calcium carbonate slurry, pulp fiber pulp, diluted pulp fiber pulp, broke, and white water. When a value or range of values based on electrical properties is predetermined, such as an optimal value or range, the introduction of carbon dioxide may be used to adjust the value so that it is closer to the predetermined value.
Description
Background of invention
The present invention relates to papermaking process and system.More particularly, the present invention relates to adjusting to electrical properties of papermaking compositions.
Mix by composition, this soliquid is flow to by narrow slit make paper on the papermaking wire-cloth multiple colloid, polymer and solution.Paper pulp is the pseudoplastic material with fine plastic yield.The size of yield stress and wherein with the mode of shearing viscosity-modifying for the steady outflow of paper and on mobile papermaking wire-cloth suitable thickness be crucial.If necessary, should monitor and adjust those flow behaviors.
Colloidal science comprises various different especially outwardly systems.Many natural and artificial products and processing procedure can have the such characteristic of colloidal dispersion.For example, the commodity as shaving cream and colored paint, the F﹠B as mayonnaise and beer, and the natural system as agricultural soil and biological cell is colloidal dispersion.
In brief, colloid is the immixture of two kinds of materials.The decentralized photo or the gel phase that are in state in small, broken bits are equally distributed by second material that is referred to as dispersion or decentralized medium.Decentralized photo can be gas, liquid or solid.The big I that is present in colloidal substance in the decentralized medium changes (The American HeritageDictionary, the 4th edition, Houghton Miflin Company, the 365th page, 2000) between about 10-10000 dust (1-1000 nanometer).It is crucial that the electric charge at next-door neighbour's colloidal grain surface place and electrostatic potential distribute.Its reason is, many transmission characteristics, the electrical conductivity of many systems for example, diffusion coefficient and mobilely determine by distribution of charges.
As noted before, paper making compositions (or paper furnish) is usually by various materials (fiber, filler etc.) and body phase composition, and described body is generally the water that comprises dissolved substance and colloid dispersed substance (salt, polymer, dispersant or the like) mutually.But the total electrical charge of whole batching (particulate and water) or mean charge must be neutral (elrectroneutrality pcharge-neutrality principles).Yet one-component can be electropositive (CATION), electronegative (anionic), or neutral.In addition, each particle will have the concrete mean charge of being derived and being obtained by many independent CATION and anionic site, and water will have " on average " electric charge that is obtained by dissolved substance and colloidal substance.
The surface chemistry performance of fiber and fiber fines depends on the chemical composition on fiber or fiber fines surface.For example, the paper pulp fiber by mechanical pulping method and/or chemical pulping method obtain will obtain certain electric charge in the time of in being scattered in water.Several ionizable groups that are present in the wood pulp are wherein arranged, as hemicellulose and lignin carboxyl, lignin phenolic hydroxyl group, sugar alcohol base, hemiacetal group and lignosulphonates group.
Fiber and fiber fines also can bring electric charge, and this depends on the kind and the concentration of dissolved substance in the water.For example, dissolving salt often has ion-exchange performance and the electric charge that obtains in paper pulp fiber can be negative electrical charge or positive charge or neutral.Absorption intensity (ionic adsorption) by carboxyl is the function of ioni valence and kind.For various ions, the sucting strength of xylon in the following order: Na
+＜K
+＜Ag
+＜Ca
2+=Mg
2+=Ba
2+＜Al
3+(William E.Scott, Wet EndChemistry, TAPPI, Ed.1996, the 16th page).
With regard to the problems referred to above, additive is important equally.Many additives of listing in table 1 have surface charge.The kind of electric charge and intensity will change based on additive therefor.These chemical addition agents comprise: retention agent, and flocculant, filter aid, resin, dispersant, chelating agent, antiscale, corrosion inhibiter, slimicide, or the like.
Table 1: wet end chemistry additive
| Internal sizing agent | The acid modified starch | Direct dyes |
| The externally sizing agent | Hydrolyzed starch | Pigment dispersion |
| Rosin is generally aliphatic organic acid, as rosin acid | Alkalescence (neutrality) sizing agent | The liquid sulfur dyestuff |
| Rosin soap (for example sodium abietate) | Alkyl ketene dimer (AKD) | Optical Bleaching Agent (OBA) |
| Starch sizing agent | Enetutanedioic acid anhydride (ASA) | The diaminobenzil disulfonic acid derivatives |
| Cereal starch (cornstarch, wheat starch) | Neutral rosin sizing agent | The OBA quencher |
| Stipes starch (for example potato starch, tapioca) | Wax (pertroleum wax or microwax) | The quaternary polyamide |
| Unmodified starch | The fluorine chemistry agent | Retention agent, filter aid |
| Modified starch | Do strong resin (as styrene-maleic anhydride copolymer, polyacrylamide polyurethane, and polyvinyl alcohol) | The single polymers system |
| Oxidized starch | Cationic flocculant | Polyacrylamide |
| Starch (anionic/cationic) | Alum (paper-makers' alum), with the alum substitute, as polyaluminium chloride, poly-aluminium hydroxide and polysilicate sulfuric acid aluminium | Diallyl dimethyl ammoniumchloride |
| Amphoteric starch | Dyestuff | Polymine |
| Starch ester | ACID DYES is used with the dyestuff sticking agent usually | Acrylic acid |
| Hydrophobic starch | Basic-dyeable fibre | The binary polymer system |
The kind of institute's water, and the change of the treatment conditions that adopted also can influence the quality and quantity of existing ion.The trend of current industry is: minimum degree ground uses fresh water during papermaking, and the increasing industrial water that circulates.The recirculation of industrial water has increased the ion that forms in the system.Dissolved charge in the water mainly is because due to the various soluble salts that exist with its ionic species, as sodium salt, and calcium salt, hydrochloride and sulfate.
The universal method of evaluation form surface charge is to measure zeta potential, rather than measures actual surface charge.Zeta potential will illustrate with at the interface charge potential between the stern layer (Stern Layer) of electric double layer and gouy-Chapman region (Gouy-Chapman region).The intensity of these current potentials and corresponding distance have been determined the ability (William E.Scott, Wet End Chemistry, TAPPI, Ed.1992,3-4 page or leaf) that the hydrophobic suspension anti-freezing is poly-or flocculate.Papermaker is usually with the indication of zeta potential as electronic state of charge in the system.
Using and measuring to papermaker of zeta potential provides some benefits.At first, for given additive, can provide the absorptive capacity of paper pulp fiber.In addition, can also help selection, thereby obtain charge balance the requirement additive types.In addition, by with the set-point deviation reduce to be used for predicted interference.
For papermaker, zeta potential is measured and some representative publication of advantage comprises: WO99/54741 A1 people such as () Goss, EP 0 079 726 A1 (people such as Evans), WO98/12551 (Tijero Miguel), with US 4,535,285 (people such as Evans), " Wet-End Chemistry of Retention; Drainage, and FormationAids ", Pulp and Paper Manufacture, Vol.6:Stock Preparation (Hagemeyer, R.W., Manson, D.W., and Kocurek, M.J., ed.), Unbehend, J.E., Chap.7:112-157 (1992), " Use ofPotentiometric Titration and Polyelectrolyte Titration toMeasure the Surface Charge of Cellulose Fiber ", Gill, R.I.S., Fundamentals Pmkg. (Baker ﹠amp; Punton, ed.) Trans.9th FundamentalRes.Symp. (Cambridge), Vol.1:437-452 (in September, 1989), " Adsorption of Ions at the Cellulose/Aqueous ElectrolyteInterface ", Harrington, T.M.; Midmore, B.R, JCS Faraday I 80, no.6:1525-1566 (in June, 1984), " SURFACE PHENOMENA ", Clark, J.d ' A, Pulp Technol.﹠amp; Trmt.for Paper (Miller Freeman Publns.), Chap.4:87-105 (1978), " ADSORPTION AND FLOCCULATION MECHANISMSIN PAPER STOCK SYSTEMS ", Britt, K.W.; Dillon, A.G.; Evans, L.A., TAPPI Papermakers Conf. (Chicago) Paper IIA-3:39-42 (in April, 1977 18-20), and ZETA-POTENTIAL MEASUREMENTS IN PAPERMANUFACTURE ", Lindstrom, T.; Soremark, C., Papier 29, no.12:519-525 (in December, 1975).
The zeta potential value of measuring during papermaking is that system relies on, and changes with the change and the interference of the condition of processing.The serious deviation of zeta potential and system optimum value will influence the production and the quality of cellulose products.Generally speaking, proposed many suggestions already, wished promptly that zeta potential was near zero or negative slightly.Yet for concrete paper machine, target zeta potential value is the function of some factors, and described factor is as batching kind, productivity ratio, product hierarchy, environmental condition, specific operator on duty, specific raw material, and additive.
Avoid or proofread and correct the zeta potential deviation or reduce dry a kind of method and be: paper-making process is regulated by the different piece/stage of additive being introduced paper-making process.Yet introducing additive has obvious defects.
At first, additive is introduced the chemical interaction that will occur in the paper-making process with Chemical composition that the unknown.It is undesirable product that unforeseen chemical reaction may form its influence to paper-making process.Owing to, therefore, be difficult to process conditions are regulated to correct bad influence to the not more understanding of these chemical reactions.
The second, along with the past of time, additive is introduced paper-making process additive will be assembled, and the gathering that will make additive and each component known response product of paper making compositions.When the concentration of described product reached higher limit, described paper-making process must stop.In this case, the operator must lose paper pulp or it is handled, so that can make paper pulp recirculation.In addition, the operator may have to make the aqueous components of paper making compositions to remove, and with fresh water and additive it is replenished again.Most importantly, seriously reduced productivity ratio.
The 3rd, additive to be introduced paper-making process also will make fiber, the physical action of the dissolved substance in colloid thing and the paper making compositions is complicated.For example, suitably do not neutralized if having the colloid of effective area electric charge, they will with the material aggregation of opposite charges, during papermaking, cause flocculation thus in the unsuitable time.On the contrary, if colloid does not have enough electric charges, promptly they still are suspended in aqueous phase, assemble and flocculate may not can to take place at reasonable time, or not can take place.
The 4th, some additive may be undesirably with described method in various mechanical parts reactions.Along with the past of time, the corrosion of these parts can cause mechanical breakdown.The result is that described method must stop and must be to described parts place under repair or replacing.This usually is very expensive.
Although above-mentioned defective, but still the many suggestions of CATION or anion chemistry additive have been proposed to add.Some suggestion has proposed for this improved different strategy.
US6, electrolyte is used in 072,309 people such as () Watson suggestion, as CATION (aluminium and the iron CATION that comprise dissolving), so that adjust zeta potential.
US5,365,775 (Penniman) have disclosed by add suitable polymers in paper-making process and have adjusted zeta potential.
" INTERFACIAL PROPERTIES OF POLYELECTROLYTE-CELLULOSESYSTEMS; " (Onabe; F.; J.Appl.Polymer Sci.23; the summary of no.10:2909-2922 (on May 15th, 1979) has disclosed: having and do not having the irreversible absorption individual layer of cationic polyelectrolyte, promptly gathering under the situation of (dimethyl diallyl ammonium chloride), Dichlorodiphenyl Acetate salt-grade dissolving pulp fiber carries out Zeta-potential and measures ELECTROKINETIC PROPERTIES OF CELLULOSE FIBERS WITHADSORBED MONOLAYERS OF CATIONIC POLYELECTROLYTE.Along with the increase of adsorpting polymerization thing amount, the negative Zeta-potential of fiber reduces, until the polarity of Zeta-potential be converted on the occasion of till.When having finished the formation of saturated monolayer, will not observe the obvious change of Zeta-potential value.This suggestion of making a summary:, control the electric charge of cellulose fibre before can forming in the saturated monolayer of cationic polyelectrolyte if when the absorption number of fragments of per unit area fiber surface is greater than the carboxyl quantity of per unit area fiber surface when saturated monolayer forms.
" COMPARATIVE EVALUATION OF ELECTROKINETIC BEHAVIOR OFPOLYELECTROLYTE-CELLULOSE SYSTEMS " (Onabe, F., J.Soc.FiberSci.Technol.Japan (Sen-i Gakkaishi) 34, the summary of no.11:T494-504 (in November, 1978) has disclosed: carry out the mechanism of electrostatic charge control and the effect of counter ion counterionsl gegenions is carried out when the control surface electric charge various researchs in order to illustrate by the CATION wet end additive in paper pulp fiber.In the system of the polymeric layer that has Irreversible Adsorption, along with the increase of salinity, the negative Zeta-potential that has a fiber of individual layer will make polarity be converted on the occasion of, and the Zeta-potential of multilayer still keeps negative value.In the system that comprises different chemical valence counter ion counterionsl gegenions, when salinity increases, the polarity of positively charged and electronegative fiber all will be changed.In two individual system of simulation wet end of machine operation, along with the increase of alum addition, electronegative fiber still keeps elecrtonegativity, but will convert positive charge to when the dosage of polyeletrolyte increases.Propose electric pair-layer model already and explained the electronic performance of system.Shown importance to the special absorption of fiber effective charge control multivalence counter ion counterionsl gegenions.
" DRAINAGE AND RETENTION MECHANISMS OF PAPERMAKING SYSTEMSTREATED WITH CATIONIC POLYMERS " (Moore, E.E., Tappi 58, and no.1:99-101 (in January, 1975) has disclosed: wherein use chemical conditioner papermaking systems the best dehydration or keep not necessarily relevant with the charging neutrality position of substrate surface.In comprising the bleached pulp suspension of alum, even fiber surface has carried out charge reversal, along with the increase of cationic-type polyacrylamide amount, can increase widely the dehydration or keep.These suggestions lack correlation with zero Zeta-potential and show: the mechanism except that charging neutrality can be controlled.
" IMPORTANCE OF ELECTROKINETIC PROPERTIES OF WOOD FIBER FORPAPERMAKING " (Lindstrom, T.; Soremark, C.; Heinegard, C.; Martin-Lof, S., Conference:TAPPI Papermakers Conf. (Boston), TAPPI Papermakers Conf. (Boston): 77-84 (June 3-6,1974)) summary has disclosed: by add the variable of cationic-type polyacrylamide (PAA) zeta potential and the trend of flocculation in cellulosic material dispersion (microcrystalline cellulose colloidal sol).Best flocculation occurs in zero zeta potential approximately.Mill is to zeta potential with on the net once by concerning between the retention that the test of measuring shows: along with the decline of zeta potential, retention will increase.
" RETENTION AND RETENTION AIDS " (Ninck Blok, C.J.J.; Klein, B.de, Papierwereld 22, no.3:69-81 (March, 1967)) summary disclosed the clear and definite relation that is adsorbed to CATION retention agent on the exposed fibers surface.As the function of cationic retention aid agent adsorbance, the Zeta-potential measured value of paper pulp fiber shows the change from negative electrical charge to the positive charge value.This article is pointed out: the retention of increase may be because the change of Zeta-potential causes.
" Online Cationic-Demand Measurement for Wet-EndPapermaking " (Veal, C., 1997 Engineering ﹠amp; Papermakers:FormingBonds for Better Papermaking Conference, (October 6,1997 for (TAPPI Press): 287-296; TAPPI Press)) summary has disclosed: by to the measurement of colloid or dissolved charge amount so that before slurry arrives the paper machine, determine or find out that the charge characteristic of batching changes, and with gain in strength performance and improve the optimal control of operability, dehydration property and evenness of cationic materials.
" Starches for Surface Sizing and Wet-End Addition " (Brouwer, P.H., Wochenbl.Papierfabr.124, (January 15 for no.1:19-23,1996)) disclosed: when at the electric charge (zeta potential) of fiber surface and the electric charge (dissolved charge) in the water all near zero the time, the wet end of machine operation will provide optimum, and suitable cationic additive (as polyacrylamide) is used in suggestion.
Also has the suggestion of some other other additive of interpolation in addition.
" Interactions Between Cationic Starches and PapermakingFibers; Effect of Starch Characteristics on Fiber SurfaceCharge and Starch Retention " (Gupta; B.Scott; W., 1995Papermakers Conference:Proceedings (TAPPI): 85-96 (April26,1995; TAPPI Press)) disclose: with regard to time-correlation, starch DS and dosage will be to influence the most important factor of surface charge, and suggestion: when selecting the starch of special-purpose, must carry out starch-retention and measure, and starch DS and dosage must be exercisable variablees.
" INFLUENCE OF ALUM AND pH ON THE ZETA POTENTIAL OF FIBERSAND ADDITIVES " (McKenzie, A.W.; Balodis, V.; Milgrom, A., Appita 23, no.1:40-4 (July, 1969)) and disclose: in the presence of aluminum sulfate, the negative electrical charge of finding on fiber, starch and titanium dioxide can reverse usually.In most cases, the reverse of electric charge is owing to be adsorbed on fiber or the lip-deep colloidal alumina of additive causes.
Beyond above-mentioned electrical property zone, because of various reasons, advised already carbon dioxide is added in the papermaking process.
WO99/24661A1 has disclosed: improve the pulp suspension fluid dewatering by handling with carbon dioxide before dewater unit just.
US2002/0092636 A1 and US6,599,390 B2 have disclosed and have added carbon dioxide so that be settled out multi-form calcium carbonate in comprising some reactors of paper pulp, and wherein said paper pulp includes calcium hydroxide or calcium oxide.
US2002/0148581 A1 has disclosed by adding carbon dioxide waste paper pH has been adjusted.
US2002/0162638 A1 has disclosed and has utilized the carbon dioxide with reduction purity that the additive in the pulp suspension is precipitated.
US2002/0134519 A1 has disclosed by carry out pH control formation metal hydroxides with carbon dioxide and has removed harmful substance.
US6,251,356 B1 have disclosed winnofil from the pressurized reactor that comprises calcium hydroxide or calcium oxide.
US6,436,232 B1 and US6,537,425 B2 have disclosed for precipitation of calcium carbonate is gone out carbon dioxide have been added in the paper pulp that comprises calcium hydroxide.
Although these publications are arranged, recognize carbon dioxide and electrical properties of papermaking compositions such as zeta potential without any publication, the interaction between electrical conductivity and the electric charge requirement.Disclosed without any publication: according to electrical property such as zeta potential to paper making compositions, the measurement of electrical conductivity and electric charge requirement and carbon dioxide is added in the paper making compositions.Add the benefit of carbon dioxide according to not recognizing for electrical properties of papermaking compositions.
Therefore, what those skilled in the art will recognize is, for electrical property such as the zeta potential of adjusting paper making compositions, and electrical conductivity, electric charge requirement, and streaming potential need more suitable additive for papermaking systems.What also will recognize in addition is that the additive that need often can not accumulate along with the past of time needn't often undesirably stop causing paper-making process.What will recognize in addition is, needs not the additive that can have side effects to the papermaking equipment parts.What also will recognize in addition is will improve fiber slurry when also needing in being added into paper-making process, the paper pulp fiber slurries of dilution, waste paper, plain boiled water, the additive of paper web and page characteristic.
Summary of the invention
One object of the present invention is to provide adjusts electrical properties of papermaking compositions such as zeta potential, the improving one's methods of electric charge requirement and electrical conductivity.Another object of the present invention is to: adopt the more suitable additive that the past along with the time often can not accumulate, provide and adjust improving one's methods of electrical properties of papermaking compositions, thereby papermaking process needn't often undesirably be stopped.Another object of the present invention is to: adopt the additive that can not have side effects, provide and adjust improving one's methods of electrical properties of papermaking compositions the mechanical part of paper machine.Another object of the present invention is to, will improve fiber slurry when adopting in being added into paper-making process, the paper pulp fiber slurries of dilution, waste paper, plain boiled water, the additive of paper web and page characteristic provides and adjusts improving one's methods of electrical properties of papermaking compositions.
For satisfying these requirements and other requirement, a kind of method of adjusting electrical properties of papermaking compositions is provided, this method comprises the steps.Provide to comprise gel phase at least a paper making compositions of water and optional paper pulp fiber.The gel phase of one of described at least a paper making compositions, each of water and optional paper pulp fiber all have electrical property and based on the corresponding value of described electrical property.Carbon dioxide is introduced in described at least a paper making compositions at least a, and its consumption is obviously adjusted with corresponding electrical property value and is as the criterion.
In addition, also provide the method for the chemical addition agent amount that a kind of reduction is added into paper making compositions, this method comprises following steps.Provide to comprise gel phase at least a paper making compositions of water and optional paper pulp fiber.The gel phase of one of described at least a paper making compositions, each of water and optional paper pulp fiber all have electrical property and based on the corresponding value of described electrical property.A certain amount of chemical addition agent is introduced in described at least a paper making compositions at least a.A certain amount of carbon dioxide is introduced in the described at least a paper making compositions that wherein adds chemical addition agent at least a, reduced the addition of chemical addition agent simultaneously.The addition of carbon dioxide is worth being as the criterion with obvious adjustment with corresponding electrical property.
Specifically, the application provides following invention:
1. method of modifying to electrical properties of papermaking compositions, described method comprises the steps: to provide at least a paper making compositions, described composition comprises gel phase, water and paper pulp fiber, and each of the gel phase of one of wherein said at least a paper making compositions, water and paper pulp fiber all has electrical property and based on the corresponding value of described electrical property; Carbon dioxide is introduced in described at least a paper making compositions at least a, and its consumption is adjusted at least 1% with corresponding electrical property value; Selection is based on the predetermined value or the predetermined range of electrical property; Measure at least a electrical property of gel phase, water and the paper pulp fiber of at least a paper making compositions, obtain a measured value thus; Measured value and predetermined value or predetermined range are compared; Selection wherein, is compared with measured value based on the carbon dioxide addition of described contrast step, and adjusted value more approaches predetermined value or predetermined range.
2. the method for heading 1, wherein: described at least a paper making compositions also comprises solid carbonic acid calcium in addition; At least a portion of solid carbonic acid calcium is dissolved when introducing the described step of carbon dioxide.
3. the method for heading 1, also comprise the steps: in addition first, second and the 3rd paper composition are elected to be described at least a paper making compositions, wherein: first paper making compositions is a pulp liquor, second paper making compositions is a waste paper, and the 3rd paper making compositions is the plain boiled water that does not comprise a large amount of paper pulp fibers; In the downstream of container, on papermaking wire-cloth, make the paper pulp fiber dehydration of first paper making compositions, and on papermaking wire-cloth, produce the second and the 3rd paper making compositions.
4. the method for heading 3 also comprises following steps: first paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide in addition.
5. the method for heading 3 also comprises the steps: second paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide in addition.
6. the method for heading 3 also comprises the steps: the 3rd paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide in addition.
7. the method for heading 3 also comprises: the dilution of first paper making compositions is obtained the 4th paper making compositions thus in addition; Described the 4th paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
8. the method for heading 3, wherein: corresponding electrical property value is based on zeta potential.
9. the method for heading 3, wherein: corresponding electrical property value is based on electrical conductivity.
10. the method for heading 3, wherein: corresponding electrical property value is based on the electric charge requirement.
11. the method for heading 3, wherein: corresponding electrical property value is based on streaming potential.
12. the method for heading 8, wherein: the corresponding zeta potential value of at least a gel phase of first, second and the 3rd paper making compositions is a negative value, and its adjustment to make it the negative value absolute value littler.
13. the method for heading 8, wherein: at least a gel phase of first, second and the 3rd paper making compositions and at least a corresponding zeta potential value of paper pulp fiber be on the occasion of, and its adjustment makes it on the occasion of littler.
14. the method for heading 9, wherein: first, second and at least a gel phase of the 3rd paper making compositions and at least a corresponding conductivity value of paper pulp fiber increase by adjustment.
15. the method for heading 10, wherein: at least a gel phase of first, second and the 3rd paper making compositions and at least a corresponding charge of paper pulp fiber need value to pass through to adjust to reduce.
16. the method for heading 1, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
17. the method for heading 8, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
18. the method for heading 1, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
19. the method for heading 14, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
20. the method for heading 15, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
21. the method for heading 1 also comprises the steps: to utilize adjusting device to control the amount of carbon dioxide of being introduced in addition, this adjusting device is finished described contrast step.
22. the method for heading 21, wherein, adjusting device comprises programmable logic controller (PLC).
23. the method for heading 3 also comprises the steps: the dilution of first paper making compositions is obtained the 4th paper making compositions thus in addition; Be provided for supplying the paper pulp pond of first paper making compositions; Provide receive the 4th paper making compositions and on across the papermaking wire-cloth upper surface flow box of dispense paper pulp fibres, described flow box is positioned at the downstream in paper pulp pond; With the position of select introducing carbon dioxide, this chosen position is in paper pulp Chi Chu or its downstream, and in the non-conterminous upstream of flow box.
24. the method for heading 3 also comprises the steps: to select zeta potential as electrical property in addition; First paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide; The fibre concentration of first paper making compositions is chosen as at least 3%.
25. the method for heading 3 also comprises the steps: the dilution of first paper making compositions is obtained the 4th paper making compositions thus in addition; Select zeta potential as electrical property; With the 4th paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
26. the method for heading 3 also comprises the steps: to select zeta potential as electrical property in addition; Second paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
27. the method for heading 3 also comprises the steps: to select zeta potential as electrical property in addition; The 3rd paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
Summary of drawings
Fig. 1 is the schematic diagram that is suitable for implementing the system of the inventive method.
Fig. 2 shows the carbon dioxide of different pH scopes and the sulfuric acid curve map to the influence of Zeta-potential.
Fig. 3 shows the curve map of the variable concentrations of different salt to the zeta potential influence.
Fig. 4 shows for the interpolation carbon dioxide of the different salt curve map to the zeta potential influence.
Fig. 5 be show by adding carbon dioxide and calcium carbonate to the zeta potential influence curve map.
Fig. 6 be when the different in flow rate carbon dioxide GCC and PCC to the curve map of zeta potential influence.
Fig. 7 is presented at the curve map that various calcium salts influence zeta potential under the carbon dioxide existence.
Fig. 8 be show the composition of pulp more not calciferous to zeta potential influence curve map.
Detailed Description Of The Invention
We are surprised to find that, carbon dioxide are introduced the different electrical property that can be used for improving each component in the composition in the paper making compositions. The adjustment of these electrical properties is for paper-making process and system, paper web, and will bring many benefits by its page of producing.
Principal benefits of the present invention is: make and improve zeta potential necessary, additional chemical agent such as starch, the minimized of polymer etc. In addition, also help the gathering of additional chemical agent in the system to minimize. For example, if so that the electronic performance variable of paper pulp and/or batching minimizes such mode when adding, it will be useful adding carbon dioxide. The well-established fact is that the electronic performance of batching dewater (during the sheet forming), and sheet properties has obvious impact for keeping. Variation of parameter as keep and dewatering can produce immediate effect to the tension force control of paper machine. This will affect dimensional stability and will form inhomogeneous web properties, and may cause disconnected paper (namely shutting down).
In the method for the invention, carbon dioxide is introduced at least a paper making compositions, wherein, each paper making compositions comprises gel phase, water and optional fiber. The gel phase of one of at least a paper making compositions, water, and optional fiber at least a has electrical property and based on the corresponding electrical property value of described electrical property. Then, be worth being as the criterion with obvious adjustment with the electrical property of measuring, introduce carbon dioxide.
Word " obviously adjust " refers to, and for the bleached pulp fiber, it is about 1% that the electrical property value is adjusted at least, perhaps for the bleached pulp fiber that is mixed with the component of finding in the plain boiled water, adjusts at least about 2%. Greater than " obviously " value, greater than about 5%, it still is within the scope of the present invention such as adjusted value for controlled electrical property value.
Preferably, implement the present invention includes at the most four kinds of paper making compositions. The first paper making compositions comprises paper pulp fiber, gel phase and water. Second and the third papermaking component be respectively waste paper and plain boiled water. The 4th kind of (choosing wantonly) papermaking component is the dilution of the first paper making compositions. Preferably, dilute to provide the 4th paper making compositions with the first paper making compositions.
Any of described paper making compositions can be the composition that its component electrical property is measured, and it also accepts the carbon dioxide introduced. In addition, described paper making compositions (electrical property of its component is measured) is different from the paper making compositions of accepting carbon dioxide. In addition, carbon dioxide is introduced in two kinds of paper making compositions at least, one of them can be or can not be the measured composition of electrical property of its component. Preferably, the second paper making compositions is the composition of accepting carbon dioxide. Preferably, the second paper making compositions is the measured composition of electrical property of wherein its component.
Described electrical property is including, but not limited to zeta potential, electrical conductivity, and the electric charge requirement, streaming potential, etc. Preferably, described electrical property is selected from: zeta potential, electrical conductivity, the electric charge requirement, streaming potential, with and both or three's combination. More preferably, described electrical property is zeta potential or electric charge requirement. Most preferably, described electrical property is zeta potential.
Electrical property and adjustment thereof can be by measuring based on the measurement mechanism of electrical property report electrical property value. Carbon dioxide can be introduced in any paper making compositions, and it is including, but not limited to: the slurries of bleached pulp fiber (dilution or undiluted); Be mixed with the slurries (dilution or undiluted) of the bleached pulp fiber of plain boiled water; Be mixed with the slurries (dilution or undiluted) of the bleached pulp fiber of waste paper; Be mixed with the slurries (dilution or undiluted) of the bleached pulp fiber of plain boiled water and waste paper; Waste paper; And plain boiled water. In addition, described measurement mechanism can be online or off-line.
Because each component of each paper making compositions all has electrical property, therefore, each of these components all has the value based on electrical property. Word " based on " including, but not limited to: by the value (analogue value) of the direct report of measurement mechanism and the arithmetic value of deriving and obtaining by the analogue value. In other words, described value is the expression of electrical property quality. For example, the electrical property of zeta potential has the value take mV as unit representation, and the electrical property of electric charge requirement has the frequent value that represents with the mL of cation or anion titrant. As another example, electrical conductivity has usually with milliSiemens (mS), microSiemens (μ S), and milliohm or microhm are the value of unit representation. As another example, streaming potential has the value take mA or streaming potential unit (SPUs) as unit representation usually.
Each electrical property of each component of each composition needn't be identical. Word " wherein, in each of at least a paper making compositions, gel phase, water, and each of optional paper pulp fiber has the corresponding electrical property value based on described electrical property ", be considered to comprise many combination/conversion. For each paper making compositions, this shows that each component (suspended solid, water, and paper pulp fiber (if comprising)) all has the value with the corresponding electrical property of its component. Do not require identical electrical property is applied on each component of described paper making compositions. For example, the electrical property of paper pulp fiber can be zeta potential, and the electrical property of water can be the electric charge requirement.
As another example, the electrical property of paper pulp fiber and water also can be identical. Also refer in addition, different paper making compositions (if comprising more than a kind of) needn't have identical electrical property with regard to corresponding component. For example, in the first paper making compositions, the electrical property of water can be electrical conductivity, and the electrical property of water can be the electric charge requirement in the second paper making compositions.
Comprise that paper pulp in the present invention is the lignocellulosic material that stands pulping process. Preferred described paper pulp is bleached. Fiber is long, columniform lignocellulosic cell, comprises with lateral opening fibre tracheid and the libriform fibre that also has simple pit. Fiber has the length that can distinguish with fiber fines. Those skilled in the art it will be appreciated that fiber fines comprises very short fiber, and fibre debris derives from by ray cell or the fragment of standard mesh screen such as 200 mesh sieve mechanical treatments.
The paper making compositions kind of the present invention expection is including, but not limited to the slurries of bleached pulp fiber; Be mixed with the slurries of the bleached pulp fiber of plain boiled water; Be mixed with the slurries of the bleached pulp fiber of waste paper; Be mixed with the slurries of the bleached pulp fiber of plain boiled water and waste paper; Waste paper; And plain boiled water. Being mixed with or not having the slurries of the bleached pulp fiber of plain boiled water and/or waste paper also can be the slurries of dilution. Dilution can be in the paper pulp pond, paper machine reserve pit, wet end pond, jordan (such as degasser, sieve and/or clarifier), flow box and therebetween any or a plurality of carrying out of position. Although dilution also can be carried out in the short circuit of paper-making process, also can during getting the raw materials ready, carry out.
Except the plain boiled water that comprises gel phase and water, each of above-mentioned paper making compositions also comprises paper pulp fiber, gel phase and water.
Colloid is the immixture of aqueous phase solid. Gel phase is uniformly distributed in aqueous phase with state in small, broken bits. Water is called as dispersion or decentralized medium sometimes. In gel phase the large I of material the 10-10000 dust or larger between change. Gel phase including, but not limited to: solid inorganic compound, part have the solid carbonic acid calcium of surfactant and/or crystal modifier, SOLID ORGANIC compound, such as polymer, water-fast liquid organic compound, fiber fines, other fiber fines, filler particles, and applying glue particle. Crystal modifier has comprised the material of " crystal seed " effect, around crystal seed, with the lime deposit that is dissolved in during the pulping process that wherein produces solid carbonic acid calcium.
The water of paper making compositions comprises the various materials that are dissolved in the water, such as cation, and anion, and the material of nothing-electric charge. Typical cation comprises Ca++ Typical anion comprises: HCO3 -And CO3 2-。
Equally also shown in Fig. 1 like that, the typical short circuit of papermaking process comprises following part. To provide to blending chest 4 from the paper pulp in paper pulp pond 1. Should be pointed out that described paper pulp is not to be in drying regime, but be paper pulp fiber, the slurry condition of gel phase and water. Therefore, described paper pulp is included in the implication of " paper making compositions ". In addition, although only described a paper pulp pond, use to be also included within the scope of the present invention more than a kind of paper pulp or more than a paper pulp pond.
Also will from other paper pulp fiber of disc filter 7, comprise the other gel phase of fiber fines, and water provide to blending chest 4 in addition. With different paper pulp, thereby gel phase and water mix the concentration that formation slightly is lower than concentration of slurry in the paper pulp pond. The slurries of the dilution that then will obtain provide to paper machine reserve pit 10, and further dilute therein and provide to wet end stock tank 13, and therein further dilution. Then the slurries that this more diluted provide to jordan 16, carry out therein degassed, screening, and/or purify. Thus refining slurries are provided to flow box 19, and therein further dilution.
At flow box 19 places, with the slurry stream cross direction profiles of diluting, making with extra care, to cause when it arrives wire-cloth 22, the whole upper surface of the slurries liquid covering wire-cloth 22 that dilutes, makes with extra care. At wire-cloth 22 places, dilution, refining slurries are dewatered, with the wet web that is provided for further processing.
Most of waters and at least some gel phases can not kept here by wire-cloth 22, but are collected as the lower surface of plain boiled water 25 from wire-cloth 22. Plain boiled water 25 is recycled to wet end stock tank 13 and disc filter 7. At least some water and gel phases that derive from plain boiled water 25 drain into the plain boiled water plain boiled water basin 34 from disc filter 7, and use it for the different piece of the paper making equipment that comprises that paper pulp is got the raw materials ready. At least part of water and gel phase that derives from plain boiled water discharged disc filter 7, in order to mix with paper pulp in blending chest 4. Plain boiled water 25 comprises gel phase (comprising fiber fines) and water.
That inappropriate wet web or dried paper web mix to provide waste paper 28 with grinding water and/or plain boiled water with discovery. Waste paper 28 is collected in waste paper system 31, and then further make with extra care therein provides to disc filter 7, and then provides to blending chest 4. At least part of waste paper is discharged disc filter 7 and is mixed with paper pulp in blending chest 4. Waste paper 28 comprises paper pulp fiber, gel phase and water.
Those skilled in the art it will be appreciated that, the electrical property that method of the present invention can be adjusted paper making compositions therein will be to implement in favourable many other papermaking systems.
If desired, described electrical property can be measured by suitable measurement mechanism. Described measurement mechanism can be off-line, as in vitro, maybe can be online. If adopt the on-line measurement device, it can be arranged on any position of said method and system. Equally, if adopt the off-line measurement device, sample can be from any position of said method and system, extract from any paper making compositions. For example, the electrical property of old paper stock fiber can be measured by in any position of finding waste paper online measurement mechanism being set, and perhaps measures by getting the waste paper sample in any position.
The existing several device that is applicable to measure zeta potential. The great majority of these measurement mechanisms use electrophoresis, streaming current, streaming potential, and any of electro-osmosis. Zeta potential measurement mechanism based on the streaming potential principle operates as follows; It comprises laboratory and industrial on-line equipment. During measuring, utilize barometric gradient that fluid is passed through by paper pulp fiber, the plunger that fiber fines and other furnish component form. Utilization is arranged on the electrode of plunger both sides, measures the streaming potential of being set up by working fluid across plunger. Utilize following formula to measure zeta potential:
ζ＝(η*Is*κ)/(ε
o*ε*ΔP)
In the formula:
ζ=zeta potential
Is=streaming potential (current potentials between two electrodes)
The electrical conductivity of κ=liquid
The viscosity of η=fluent solution
ε
o=electric field constant
The dielectric constant of ε=liquid
Δ P=is across the liquid pressure drop of plunger
Existing some kinds of suitable measurement mechanisms that are suitable for measuring the electric charge requirement.As those skilled in the art be to be understood that, the electric charge requirement is: with the amount of sample titration to the required charged titrant of zero potential.The electric charge requirement can be measured polymer in the sample, colloid, and fine particle, and dissolved anion or CATION any or more kinds of charge characters.
A kind of suitable device that is used to measure the electric charge requirement is Particle ChargeDetector PCD-03.It must be noted that although this device and measurement provide the electric charge of " particle ", the electric charge requirement of this apparatus and method actual measurement sample in many cases, is measured the electric charge requirement of dissolved ions material.Although PCD can be used for the paper making compositions of all kinds, it usually is used for the sample that has wherein filtered out paper pulp fiber is measured, as the filtrate of pulp liquor, and waste paper filtrate, and plain boiled water.
The measurement of being undertaken by PCD-03 is based on following principle.Center part is the plasticity measuring unit that has suitable displacement plunger.If aqueous sample is full of the measuring unit words, molecule will be on the plastic surface that is adsorbed on plunger under the effect of Van der Waals force and on the cell membrane.Counter ion counterionsl gegenions are still free relatively.Between cell membrane and plunger, provide limited narrow crack.By motor-driven, plunger vibrates in measuring cell and produces strong liquid stream, and liquid stream is taken away free counter ion counterionsl gegenions, so from the sample material of absorption it is isolated.At the built-in electrode place, counter ion counterionsl gegenions induce electronic calibration and amplified current.Streaming current is displayed on the display that has appropriate signals.
For sample is carried out quantitative charge measurement, have to carry out the polyeletrolyte titration, it uses streaming current to determine zero point (0mV).Effectively titrator comprises Mutek TitratorPCD-02 Version 1.
Utilize titrator, be added in the sample as the polyeletrolyte of titrant with known charge density, oppositely charged.The existing electric charge of charging neutrality sample of titrant.Stop titration once reaching zero point (0mV).Measuring agent consumption (mL) is to constitute the measured value that further calculates the basis.For anionic species, used titrant for example is PDDA (Poly-Dadmac) 0.001N.
Calculate than quantity of electric charge q[eq/g according to following formula]:
q＝(V*c)/wt
Wherein:
The volume of titrant (L) that V=consumes
C=titrant concentration [eq/L]
The weight of Wt=sample [g]
If some identical samples are compared, needn't calculate quantity of electric charge q, precondition is that sample carries out titration under the same conditions, promptly carries out titration under identical sample weight and titrant concentration.In this case, can directly use the measurement volumes (mL) that consumes titrant, and the value that is obtained is directly contrasted.Here, the anion of term sample and CATION requirement are general.
No matter select which kind of measurement mechanism, it all can be used for monitoring the value of electrical property, so that utilize minimum cost of material maintenance or improve high-quality production.Yet even monitor electrical property carefully, if adjust based on the inappropriate words of the method for electrical property value, these measured values are also not too useful.In order to address this problem, we are surprised to find that, carbon dioxide can be introduced in any of paper making compositions, so that adjust the electrical property value of being inquired into.Carbon dioxide can advantageously be used for undesirable value for a certain reason is adjusted to more satisfied value.In addition, it can also be used to the electrical property value is adjusted to the scope of predetermined value or certain value, for example, and optimum value that those skilled in the art confirm or the optimum value of determining by model.
As gaseous carbon dioxide (CO
2 (g)) introduce in the Aquo System, as in the paper making compositions time, shown in following reaction, portion C O
2 (g)Free CO will be dissolved into
2 (aq):
CO
2(gas)CO
2(aq)
Work as CO
2When being dissolved in the water, it forms carbonic acid (H with aquation
2CO
3).Should be pointed out that this reaction slow (Ionic Equilibrium-Solubility and pHCalculations " (J.N.Butler, John Wiley ﹠amp; Sons, INC., 1998, chapter 10, p.365)).Shown in following reaction, H
2CO
3Can resolve into H
+And HCO
3 -Ion:
H
2CO
3H
++HCO
3 -
To paper pulp fiber, the generation of these ions was crucial when the electrical property of paper pulp fiber fines and colloid was adjusted.
By being suitable for that any method that gas is introduced in the paper making compositions is introduced carbon dioxide, described method is including, but not limited to pressurization or spray process.
As implementing example of the present invention, can make positive zeta potential on the occasion of less.By any specific theory bundle clothes, we believe, carbon dioxide aquation and separate the HCO of the dissolving that is produced subsequently in water
3 -Ion will be attracted on the positively charged paper pulp fiber and/or colloid, and positive zeta potential value is descended.In theory, attraction will continue, until reaching zero zeta potential.According to solving the previous trial of zeta potential control problem, it is favourable introducing carbon dioxide, and this is because introduce the interpolation that carbon dioxide is used for minimizing to adjust the chemical addition agent of zeta potential.If carbon dioxide is not introduced and the required nondecreasing words of additive, these additives often will accumulate in paper-making process, cause above-mentioned defective.
As another example, can make negative zeta potential negative value absolute value littler.Those skilled in the art usually are that in some position of paper-making process, zeta potential is unacceptablely low with observed.This often thinks the deviation safeguarded, disturbs or cause.In this case, carbon dioxide may be used for making effectively the so excessively zeta potential rising of negative value.
In addition, by the amount of introducing carbon dioxide is controlled, those skilled in the art can be adjusted to zeta potential the zeta potential scope of hope, perhaps even be adjusted to the separation zeta potential.Surprisingly, we find, change for given pH value, and zeta potential can be adjusted by the additive capacity bigger than conventional additive by carbon dioxide.
According to disclosed the present invention, those skilled in the art will be familiar with and understand: when carrying out paper-making process, how by utilizing the knowledge that is developed, in a part or a plurality of part of paper-making process zeta potential is controlled and/or adjusted.Similarly, they can diagnose the deviation or the system interference of zeta potential.
Similarly, can implement the present invention according to the electric charge requirement.If it is unacceptably high, carbon dioxide is introduced in the paper making compositions and will obviously be reduced total requiremants surprisingly.
Similarly, the present invention can implement according to electrical conductivity.Astoundingly, carbon dioxide is introduced to be made it surprisingly in the paper making compositions to increase.
Those skilled in the art it will also be understood that, similarly can adjust or control streaming potential.
When having calcium salt, especially during calcium carbonate, these adjustment can with in addition more wonderful mode finish.If the form difference of calcium carbonate, as winnofil (PCC) to powdered whiting (GCC), the result that can obviously not change when having calcium carbonate to be obtained.
In addition, when at calcium carbonate serosity when introducing carbon dioxide in the calcium carbonate serosity before pulp slurry is mixed, the present invention also will have astonishing adjustment to pulp slurry.When carrying out described operation, to compare with introducing calcium carbonate under the situation that does not have carbon dioxide, the zeta potential adjustment that obtains will more cater to the need.
Embodiment
Specimen preparation
In first group of experiment, use two kinds of different pulp slurry and be designated slurries 1 and slurries 2.
Slurries 1: (Derwent, B.C. Canada) obtain to be used for producing the chemical pulping of these slurries and leaf wood (HW) and needlebush (SW) paper pulp of bleaching by Econotech Service.Used paper pulp comprises northern hardwood pulp, i.e. poplar slurry and northern softwood pulp.Utilization is made with extra care the pulpboard that obtains based on the Valley beater of tappi test method no (T200sp-96).Respectively hardwood pulp and softwood pulp are refined into 450 and 430 Canadian Standard Freeness (CSF).
Utilize the ratio of 60%HW and 40%SW to prepare the pulp slurry 1 of 0.5% concentration (Cy).Utilize deionized water to prepare pulp slurry.The mixer that is used for preparing slurries is " Square D " mixer that derives from IECControls.The mixed paper slurries that obtain 3 ℃ of storages.Before experimentizing, make these slurries steadily to room temperature (20 ± 2 ℃).
The initial performance of slurries 1 is shown among the table 2A.
Table 2A: slurry content
| | Kind | 1 | |
| Concentration | 0.5％ | 4.0 | |
| HW content | |||
| 60％ | 69％ * | ||
| SW content | 40％ | 31％ * | |
| Recirculation | 0％ | 100％ | |
| Content of ashes | na | 16.5％(525℃) *，9.8％(900℃) * |
Measure by Econotech Services
By make unworn standard copy paper again pulp produce slurries 2.In LamortPulper de Laboratoire, make the Office Max PremiumQuality Copy Paper pulp again of 500 pages of bags.The specification of copy paper is:
The perforation of 3-hole
8.5 the size of * 11 letter-size, white
20# is quantitative
84 brightness
Do not contain acid
Prepare slurries 2 in the pulp machine again by restraining copy papers and amount to 12.0 liters of hot tap-waters introducing Lamort with 1503.During pulp is handled again, utilize two mixing velocity settings: (1) high (total incorporation time: 2 minutes) and (2) low (total incorporation time: 8 minutes).In pulp process again, change the order of mixing velocity.What this means? utilize deionized water to make pulp slurry dilution again, thereby production concentration is 4.0% slurries 2.
The initial performance of slurries 2 is shown among the table 2B.
Table 2B: the size performance of measurement
| | Kind | 1 | |
| pH | 5.35 | 8.90 | |
| Electrical conductivity | 0.0121mS | 0.089mS | |
| Zeta potential | -127.3mV | -45.3mV | |
| The inlet current potential | 8.44mV | 3.04mV | |
| Pressure | 0.201 crust | 0.219 crust |
* be equivalent to the size performance that records at different time (being identical slurries discontinuous measurement) in the initial slurry performance (mean value) shown in this table.When preparing slurries, almost without any electrical conductivity with deionized water.Therefore, this will cause the zeta potential of special negative value.
In second group of experiment, use two kinds of different solution.First solution is made up of wet end filtrate (filtering by 200 orders).Second solution is made up of the dilution (diluting with deionized water) of 5 times of pulp mill's plain boiled waters.(Beaupre Quebec) provides described solution/filtrate by Abitibi-Consolidated.Undiluted plain boiled water has high electrical conductivity and anionic charge correspondingly.Because relatively low electrical conductivity and anionic charge is more suitable for measuring with corresponding measurement mechanism, therefore with 5 times of plain boiled water dilutions.The table 2C that the reference solution performance is used.
Table 2C: the performance of pulp mill's filtrate and dilution plain boiled water
| Pulp mill's filtrate character | Dilution plain boiled water character | |
| Temperature | 21.5℃ * | 22.6℃ * |
| pH | 7.92 | 8.18 |
| Electrical conductivity | 5420μS/cm | 1391μS/cm |
| TDS | 4500ppm(442) | 962.4ppm(442) |
| PCD (10.0mL sample) [diluting 5 times] | 11.976mL?Poly-Dadmac (0.001N) | 8.594mL?Poly-Dadmac (0.001N) |
* the temperature of sample during analyzing.
Experimental condition: repeatability and reproducibility
The zeta potential measurement mechanism that is used for testing is: " Mutek-model no.SZP06 " instrument derives from BTG Industries, Norcross, GA.In estimating the repeatable trial of Mutek device (SZP-06), get five measured values of same sample (500.0 gram).For this repeatability test, the NaOH (1.019N concentration) that utilizes Aldrich to provide is with the pH regulator to 10.65 of slurries 1.The results are shown in Table 3.
The repeatability of table 3:Mutek SZP-06
| Reading | Zeta potential (mV) | Electrical conductivity (mS) | Pressure (crust) | Inlet current potential (mV) |
| 1 | -102.5 | 0.151 | 0.195 | 5.79 |
| 2 | -101.9 | 0.150 | 0.195 | 5.76 |
| 3 | -102.3 | 0.149 | 0.195 | 5.79 |
| 4 | -102.4 | 0.148 | 0.197 | 5.86 |
| 5 | -100.4 | 0.147 | 0.196 | 5.72 |
| On average | -101.9 | 0.149 | 0.196 | 5.78 |
| Standard deviation | 0.87 | 0.002 | 0.001 | 0.051 |
In the trial of estimating Mutek device reproducibility, utilize the various sample (5) of the identical slurries preparation of Mutek measurement device (slurries 1).For this specific sample, with CaCO
3(winnofil-PCC) be added in the slurries.In the IEC mixer, slurries were mixed 90 minutes altogether with 900rpm.PCC with 15% is added in the slurries based on initial bone dry fiber.
Table 4A: the reproducibility that utilizes slurries I Mutek SZP-06
| Reading | Zeta potential (mV) | Electrical conductivity (mS) | Pressure (Bar) | Inlet current potential (mV) |
| 1 | -44.0 | 0.101 | 0.209 | 2.79 |
| 2 | -43.6 | 0.102 | 0.207 | 2.73 |
| 3 | -43.2 | 0.102 | 0.207 | 2.71 |
| 4 | -44.2 | 0.101 | 0.206 | 2.76 |
| 5 | -42.9 | 0.101 | 0.213 | 2.77 |
| On average | -43.6 | 0.101 | 0.208 | 2.75 |
| Standard deviation | 0.54 | 0.0005 | 0.003 | 0.032 |
In the other trial of estimating Mutek device reproducibility, measure five parts of paper pulp with the dilution of pulp mill's plain boiled water.Described paper pulp is the HW of above-mentioned chemical pulping and bleaching and the mixture of SW slurry 80/20.In the IEC mixer, the slurries that obtain were mixed 10 minutes altogether with 900rpm.
Table 4B: utilize reproducibility with the paper pulp Mutek SZP-06 of plain boiled water dilution
| Beaker | Zeta potential | Electrical conductivity | Pressure | Streaming potential mV | Average mV signal changes | Average pressure changes |
| 1 | -29.4 | 4.49 | 203 | -0.361 | 0.004 | 0.966 |
| 2 | -32.5 | 4.44 | 204 | -0.405 | 0.004 | 0.931 |
| 3 | -33.7 | 4.44 | 201 | -0.415 | 0.005 | 1 |
| 4 | -36.1 | 4.29 | 202 | -0.459 | 0.006 | 0.724 |
| 5 | -32.1 | 4.23 | 203 | -0.415 | 0.003 | 1.172 |
| 6 | -32.5 | 4.31 | 204 | -0.416 | 0.003 | 0.897 |
| On average | -32.717 | 4.37 | 202.83 | -0.41 | 0.004 | 0.948 |
| Standard deviation | 2.1858 | 0.104 | 1.17 | 0.03 | 0.001 | 0.146 |
The effect that slurries pH changes
Carry out two kinds of tests, with the influence of investigation pH change to the slurries zeta potential.For these two kinds of tests, utilize the pH regulator to 10.20 of the NaOH (NaOH) of 1.019N with slurries 1.
At first, the sulfuric acid (deriving from Aldrich) of the 0.1N that increment is added is added in the 500 gram slurries (slurries 1).After the acid of each increment is added, utilize Caframo mixer (RZR-2000 type) slurries to be mixed 2 minutes in 700rpm.In case sample fully mixes, just measure the pH value, and determine zeta potential, electrical conductivity, inlet current potential, and pressure with the Mutek device.
The second, with gaseous carbon dioxide (CO
2) (deriving from Air Liquide) change the pH value of slurries.Utilize mass flow controller (model MKS type 246B derives from MKS Instruments) to regulate the flow velocity of carbon dioxide, and be conducted in the described solution by stainless steel " dipping " pipe with 1/4 inch.For different time and CO
2Flow velocity utilizes laboratory mixer (RZR-2000 type) at 200rpm paper pulp to be mixed (CO
2Flow velocity and spray time are referring to table 5).
Table 5:CO
2Interpolation is to the influence of zeta potential
| Sample | CO 2(variable flow rate) | Time | CO 2(accumulation) | pH | Zeta potential |
| (mL/min) | (min) | (mL) | (mV) | ||
| 1 | na | na | na | 10.20 | -113.0 |
| 2 | 50 | 2 | 100 | 6.53 | -111.4 |
| 3 | 50 | 3 | 250 | 6.08 | -107.7 |
| 4 | 100 | 3.25 | 565 | 5.76 | -106.8 |
| 5 | 350 | 5 | 2315 | 5.50 | -106.2 |
| 6 | 1000 | 6.5 | 8815 | 5.10 | -103.5 |
| 7 | 1400 | 4.5 | 15115 | 4.70 | -96.7 |
| 8 | 2000 | 4.5 | 24115 | 4.68 | -92.3 |
| 9 | 2000 | 4.5 | 33115 | 4.65 | -91.0 |
By the result of Fig. 2 as can be seen, when using H
2SO
4When coming the acidifying slurries, zeta potential will be undergone mutation at about 5.0 o'clock at slurries pH.Yet previous acidifying (pH from 10.20 to about 5.0) is not obvious to the influence of zeta potential.
With CO
2Be added in the slurries and also will improve zeta potential.Yet in these trials, only possible is, makes pH reduce to 4.65 from 10.20, and this is because carbonic acid is weak acid.After pH4.65, add CO
2PH will be descended, and observe zeta potential and can not increase.
Surprisingly, result same as shown in Figure 2 shows: in the scope of pH10.20-4.65, and with regard to the zeta potential that improves slurries, CO
2Compare H
2SO
4More effective.In the significant pH of papermaking (4-8) scope, when using CO
2The time, for the unit change of pH, the improvement of zeta potential will be greater than using H
2SO
4In addition, for CO
2Compare and pass through H
2SO
4The identical zeta potential that obtains is by using H
2SO
4Adjusting require the very large decline of pH.To influence many other the conditions of wet end because pH changes, maybe will the short circuit of paper-making process to be exerted an influence.Therefore, it is apparent that, implement the present invention and will produce such result, described result with by interpolation H
2SO
4The result that conventional method obtained to compare to be beyond thought.
In order to detect the influence of slurries original ph, utilize the slurries I that does not carry out pH regulator to be similar to above-mentioned two experiment.Utilize CO
2The increment that carries out pH improves.The condition of slurries that pH regulator is carried out in the experimental condition that is used for experimentizing and as discussed previously being used for is identical.Comparing result is listed in the table 6.Should be pointed out that the result who in table 6, has also comprised table 5, so that demonstrate the difference aspect initial pH regulator.
As in the data as shown in the table 6, add carbon dioxide the favourable influence of zeta potential is not relied on original ph or pH scope.
Table 6: when with CO
2When providing to slurries, the influence of initial pH.
| Sample | CO 2(mL) | pH | Zeta potential (mV) | CO 2(mL) | pH | Zeta potential (mV) | |
| 1 | 0 | 5.04 | -129.0 | 0 | 10.20 | -113.0 | |
| 2 | 200 | 4.65 | -121.0 | 100 | 6.53 | -111.4 | |
| 3 | 400 | 4.60 | -125.5 | 250 | 6.08 | -107.7 | |
| 4 | 600 | 4.53 | -125.3 | 565 | 5.76 | -106.8 | |
| 5 | 1200 | 4.41 | -122.3 | 2315 | 5.50 | -106.2 | |
| 6 | 2400 | 4.27 | -122.1 | 8815 | 5.10 | -103.5 | |
| 7 | 4800 | 4.19 | -116.0 | 15115 | 4.70 | -96.7 | |
| 8 | ----- | ----- | ----- | 24115 | 4.68 | -92.3 | |
| 9 | ----- | ----- | ----- | 33115 | 4.65 | -91.0 |
Salt is added into the effect in the slurries
Also carry out an experiment in addition so that the influence of salt pair zeta potential is added in investigation.With potassium chloride (KCl), sodium chloride (NaCl), calcium chloride (CaCl
2), and aluminium chloride (AlCl
3) salting liquid be added among the slurries I.Be preparation potassium chloride, sodium chloride, and calcium chloride solution will be dissolved in the deionized water by the SILVER REAGENT chemical agent that FisherScientific provides.Liquor alumini chloridi is provided by LabChem.The aluminum concentration of liquor alumini chloridi is by Graphite Furnace AtomicAbsorption Spectrometer (GFAA), and the SIMAA 6000 that promptly derives from Perkin Elmer determines.The concentration of obtained solution is shown in Table 7.
Table 7: the concentration of prepared salting liquid
| Compound | Concentration of salt solution |
| KCl | 0.5mol/L |
| NaCl | 0.5mol/L |
| CaCl 2 | 0.5mol/L |
| AlCl 3 | 13500ppm (in Al) |
Prepared solution is added in the 500.0 gram slurries samples (slurries 1), and utilizes Caframo mixer (RZR-2000 type) to mix 5 minutes at 700rpm.After the mixing, measure zeta potential with the Mutek device.The result diagrammatically is shown among Fig. 3.
As shown in Figure 3, the zeta potential of slurries will change according to the kind of used salt, more particularly will change according to corresponding cationic price.These results with by the similar experiment that other approach carried out consistent (1979, page 40 for A.M Scallan and J.Grignon, SvenskPapperstidning nr2).Some viewpoint is pointed out, CATION is attracted on the electronegative outer surface of fiber in the suspension, and depend on its electric charge and hydration diameter, double-deck thickness is with contraction or expansion (Cohen, W.E., Farrant, G.and Watson, A.J.:Proc.Aust.Pulp Paper Ind.Tech.Assoc.3 (1949) 72).
Also experimentize so that investigate CO in addition
2With the influence of interpolation salt (sodium chloride and calcium chloride) to zeta potential.In these experiments, the sodium chloride of 8.8mL, 0.5mol/L and the solution of calcium chloride are added into (sodium chloride and the calcium chloride that are equivalent to 0.0044mol) among the slurries I.Then, utilize the Caframo mixer, mixture was mixed 5 minutes in 700rpm.Utilize 1/4 inch stainless steel " dipping " pipe that the carbon dioxide gas introducing is comprised in the slurries of salt.CO
2Flow velocity remain on 500 ml/min.At 200rpm slurries are mixed, meanwhile add CO
2The results are shown among Fig. 4.It should also be noted that in addition that in Fig. 4 the experiment that is marked as Comparative Examples is equivalent to not to the slurries that wherein add salt.
The result shows: no matter whether salt exists, add carbon dioxide and all can regulate zeta potential.
Add the effect of calcium carbonate
Utilize slurries 1 to carry out these experiments.The NaOH that utilizes 1.019N is adjusted to 10.65 with the original ph of slurries.Regulate the pH value of slurries, so that make CaCO in the slurries
3Decomposition minimum.With CaCO
3Be added in 500.0 slurries that restrain (0.5% concentration).Then, utilize the Caframo mixer, slurries were mixed 5 minutes in 700rpm.Utilize the MutekSZP-06 instrument to measure subsequently; Also measure pH in addition.Oven-dry weight with paper pulp is a benchmark, adds GCC and PCC.The results are shown in Table 8.Powdered whiting (GCC) derives from OMYA (Omyafil), and winnofil (PCC) derives from Specialty Minerals Inc (Albacar HO# (A-8-124-32)).
Table 8: calcium carbonate is to the influence of zeta potential
| Kind | Ash content, % | pH | ζmV | Electrical conductivity (mS) | Pressure (Bar) | Inlet current potential (mV) |
| Initially | 0 | 10.65 | -101.9 | 0.149 | 0.196 | 5.78 |
| GCC | 5 | 10.29 | -88.7 | 0.154 | 0.200 | 5.11 |
| 10 | 10.21 | -96.2 | 0.151 | 0.201 | 5.61 | |
| 15 | 10.03 | -100.6 | 0.112 | 0.207 | 6.17 | |
| 30 | 9.88 | -102.4 | 0.132 | 0.207 | 6.20 | |
| PCC | 5 | 9.90 | -98.2 | 0.113 | 0.207 | 6.06 |
| 10 | np | np | | np | np | |
| 15 | 10.06 | -108.5 | 0.114 | 0.203 | 6.59 | |
| 30 | 9.90 | -111.7 | 0.114 | 0.196 | 6.55 |
Np: do not measure
As mentioned above, add PCC or GCC and tend to increase zeta potential at the beginning, can make it then to reduce.Similarly, add PCC or GCC and tend to increase electrical conductivity at the beginning, can make it then to reduce.Similarly, PCC or GCC are added into and introduce the not uncertainty of desired amount can in the paper-making process zeta potential or electrical conductivity.
The effect of calcium carbonate and carbon dioxide
Utilize slurries 1 to carry out these experiments.With two kinds of different types of calcium carbonate (CaCO
3) be used for experiment, so that determine its influence to zeta potential.Powdered whiting (GCC) derives from OMYA (Omyafil), and winnofil (PCC) derives from Specialty MineralsInc (Albacar HO# (A-8-124-32)).
With CaCO
3Be added in the 500.0 gram slurries (0.5% concentration), and utilize the Caframo mixer slurries to be mixed 5 minutes at 700rpm.Relatively the calcium carbonate (GCC) of paper pulp 15% is to be benchmark with the initial oven dry weight of paper pulp, and adds all calcium carbonate before adding carbon dioxide.Utilize 1/4 inch ground stainless steel " dipping " pipe, introduce carbon dioxide gas with the flow velocity of 500 ml/min.During carbon dioxide is added into slurries, utilize the Caframo mixer sample to be mixed in 200rpm.Utilize Mutek SZP-06 instrument to measure subsequently; Also measure pH in addition.The results are shown in Table 5.
In order to add CO
2In time, compare the kind and the source of calcium carbonate, utilizes PCC to compare experiment.Carbon dioxide is added flow velocity is fixed on 500 ml/min, and with the initial concentration of PCC with respect to paper pulp oven dry weight stuck-at-5%.Comparing result between GCC and PCC is listed among Fig. 6.
In order investigating carbon dioxide to be introduced influence in the slurries contain different PCC and GCC amount, to experimentize with the previous sample of discussing (referring to table 8).At experimental session, add carbon dioxide: 200mL and 2400mL with two kinds of different consumptions.For the experiment of the 200mL carbon dioxide being introduced in the slurries sample, flow velocity is 250 ml/min; And for the experiment of the 2400mL carbon dioxide being introduced in the slurries sample, flow velocity is 500 ml/min.Utilize the Caframo mixer that slurries are mixed.As mentioned before, adding CaCO
3Mixing velocity therebetween is 700rpm, 5 minutes.During adding carbon dioxide, mixing velocity is fixed on 200rpm.These result of experiment are listed in table 9 and 10.
Shown in data, not only we find, introduce the zeta potential that carbon dioxide can have advantageously and regulate astoundingly slurries, and we find that also when slurries comprise solid carbonic acid calcium, its result will be more beyond thought.In this case, zeta potential will increase.In addition, although will reduce influence to zeta potential by adding solid carbonic acid calcium, carbon dioxide will make this reduction the influence reverse but also far not so far.In addition, we also find, under the situation that has solid carbonic acid calcium, carbon dioxide can not rely on the form of solid carbonic acid calcium to the influence of zeta potential, as PCC to GCC.
Table 9: in the presence of PCC, add CO
2Effect
| Sample | pH | ζ (mV) | Electrical conductivity (mS) | Pressure (Bar) | Inlet current potential (mV) |
| 0.5%Cy paper pulp | 10.65 | 101.9 | 0.149 | 0.196 | 5.78 |
| Add CaCO3-PCC (5% ash content) | 9.90 | -98.2 | 0.113 | 0.207 | 6.06 |
| 200mL?CO2 | 7.74 | -55.1 | 0.139 | 0.207 | 3.34 |
| 2400mL?CO2 | 6.16 | -20.3 | 0.345 | 0.206 | 1.05 |
| Add CaCO3-PCC (15% ash content) | 10.06 | -108.5 | 0.114 | 0.203 | 6.59 |
| 200mL?CO2 | 7.88 | -54.7 | 0.146 | 0.205 | 3.26 |
| 2400mL?CO2 | 6.62 | -13.0 | 0.599 | 0.199 | 0.54 |
| Add CaCO3-PCC (30% ash content) | 9.90 | -111.7 | 0.114 | 0.196 | 6.55 |
| 200mL?CO2 | 8.00 | -40.4 | 0.156 | 0.199 | 2.32 |
| 2400mL?CO2 | 6.53 | -10.1 | 0.635 | 0.203 | 0.42 |
Table 10: in the presence of GCC, add CO
2Effect
| Sample | pH | ζ (mV) | Electrical conductivity (mS) | Pressure (Bar) | Inlet current potential (mV) |
| 0.5%Cy paper pulp | 10.65 | -101.9 | 0.149 | 0.196 | 5.78 |
| Add CaCO3-GCC (5% ash content) | 10.29 | -88.7 | 0.154 | 0.200 | 5.11 |
| 200mL?CO2 | 8.16 | -73.0 | 0.110 | 0.198 | 4.34 |
| 2400mL?CO2 | 6.16 | -24.6 | 0.328 | 0.204 | 1.26 |
| Add CaCO3-GCC (10% ash content) | 10.21 | -96.5 | 0.151 | 0.201 | 5.61 |
| 200mL?CO2 | 8.60 | -77.1 | 0.113 | 0.201 | 4.64 |
| 2400mL?CO2 | 6.45 | -22.6 | 0.411 | 0.204 | 1.09 |
| Add CaCO3-GCC (15% ash content) | Na | -100.6 | 0.112 | 0.207 | 6.20 |
| 200mL?CO2 | 8.02 | -56.0 | 0.131 | 0.206 | 3.40 |
| 2400mL?CO2 | 6.32 | -18.6 | 0.488 | 0.204 | 0.87 |
| Add CaCO3-GCC (30% ash content) | 9.88 | -102.4 | 0.132 | 0.207 | 6.20 |
| 200mL?CO2 | 8.32 | -66.8 | 0.135 | 0.205 | 4.02 |
| 2400mL?CO2 | na | -20.7 | 0.558 | 0.207 | 0.92 |
We have also investigated the influence of " minimizing " carbon dioxide interpolation to slurries in addition.Utilize slurries 1 to carry out following experiment.To be added in the slurries based on the PCC of the fixed dosage of absolute dried paper pulp weight 15%.Utilize the IEC mixer, PCC and slurries (10000 gram) were mixed 90 minutes in 900rpm.After the preparation slurries, carbon dioxide is added in the 500g sample of slurries/PCC mixture.The carbon dioxide flow velocity is fixed on 50 ml/min (by 1/4 inch " dipping " pipe), and during adding carbon dioxide, utilizes the Caframo mixer to mix in 200rpm.
Table 11: the change of zeta potential in the presence of calcium carbonate
| Time (second) | Zeta potential (mV) | Electrical conductivity (mS) | Pressure (bar) | Inlet current potential (mV) | Remaining Ca ++Concentration (ppm) |
| 0 | -43.6 | 0.101 | 0.208 | 2.75 | ?--- |
| 10 | -36.3 | 0.121 | 0.199 | 2.15 | ?15 |
| 20 | -35.1 | 0.132 | 0.198 | 2.05 | ?18 |
| 30 | -34.3 | 0.145 | 0.206 | 1.94 | ?20 |
| 40 | -33.7 | 0.148 | 0.202 | 1.98 | ?22 |
| 50 | -33.2 | 0.154 | 0.202 | 1.94 | ?24 |
| 60 | -31.7 | 0.163 | 0.202 | 1.84 | ?26 |
| 90 | -28.5 | 0.186 | 0.202 | 1.62 | ?28 |
| 120 | -25.9 | 0.211 | 0.202 | 1.44 | ?31 |
The calcium ion-selective electrode (ISE) that utilization is distributed by Cole-Parmer Instruments (#24502-08); IONS 5meter with deriving from Oakton measures remaining Ca
2+Concentration.Should be pointed out that before utilizing calcium ISE, utilize 0.45 micron filter (deriving from Pall Gelman Laboratory) that sample is filtered.Astoundingly, these results show that when the carbon dioxide volume increases (as by shown in the time), zeta potential and electrical conductivity also will increase.In addition, remaining Ca
2+Concentration also will increase.
At CO
2There is the effect of various calcium salts down:
In Fig. 7, utilize and wherein use all previous experimental datas of discussing that contain calcium salt to map.In addition, the experimental result that also calcium acetate (0.5mol/L solution) wherein is added in the slurries is mapped.Should be pointed out that a fixing variable is the calcium amount (concentration) that is added in 500 gram slurries, 1 sample in these experiments.In all experiments that are shown in Fig. 7, the calcium amount that is added in the 500 gram slurries samples is 0.0044 mole.As previous experiment, the flow velocity of carbon dioxide is fixed on 500 ml/min.After adding calcium acetate, utilize the Caframo mixer, in 700rpm mixture was mixed 5 minutes.During adding carbon dioxide, mixture is mixed in the speed of 200rpm.
As shown in Figure 7, when calcium salt exists, add carbon dioxide and will adjust/increase zeta potential unexpectedly.More beyond thoughtly be that when solid carbonic acid calcium (PCC or GCC) when existing, zeta potential will obviously increase.
Add the influence of carbon dioxide to the recirculation batching:
In order to investigate to adding CO in the pulp slurries again
2Effect, use slurries 2.What need emphatically point out is that calcium carbonate is not added in these samples.In these experiments, carbon dioxide is added in the slurries by utilizing 1/4 inch stainless steel " dipping " pipe.CO
2Flow velocity remain on 750 ml/min.The first observed that can carry out is: the zeta potential of system compares with slurries 1 that relatively low (average-127.3mV is on average-45.3mV).This is understandable, because the pulp slurries comprise quite a large amount of ash content (being pearl filler) again.In addition, use running water (hard water) (that is, producing the slurries of 10%Cy) for pulp process again.Data are shown among Fig. 8.
Astoundingly, add carbon dioxide and not only adjust/increased by paper pulp, contain calcium salt paper pulp, contain the zeta potential of the slurries that calcium carbonate paper pulp makes, and also be like this as waste paper for the recirculation batching.
With carbon dioxide is added in the calcium carbonate before slurries mix:
In addition, we are also to being added into carbon dioxide the influence in the calcium carbonate serosity before calcium carbonate serosity is introduced paper pulp.
At first, the mixture of preparation 60/40HW/SW (its performance is referring to table 2B).Then, preparation 10% calcium carbonate (PCC) slurries (deionization not in use PCC), and be divided into five parts of samples of 200 milliliters every part.Then, the constant carbon dioxide flow velocity with 500 ml/min is added into carbon dioxide in the PCC slurries sample of 200 milliliters of each parts.During adding carbon dioxide, the PCC slurries are mixed (utilize the Caframo mixer, model is RZR-2000) with 400rpm.Utilize mass flow controller (model MKS type 246B derives from MKSInstruments) to regulate the flow velocity of carbon dioxide, and be conducted in the described solution by stainless steel " dipping " pipe with 1/4 inch.For 4 samples wherein, the carbon dioxide volume that inquiry agency adds.The 5th part of sample is used as Comparative Examples, and do not receive any carbon dioxide.The volume of carbon dioxide is respectively: 500mL CO
2, 2500mL CO
2, 7500mL CO
2With, 14000mL CO
2
Then, with 2.5mLPCC/CO
2Slurries are added in four part of 500 pulp liquor sample that restrains of 0.5%Cy.After adding PCC, utilize the Caframo mixer, in 700rpm the slurries that obtain were mixed 10 minutes.Then, utilize Mutek SZP device that sample (pulp liquor) is analyzed.Also pH and temperature are measured in addition.The results are shown in Table 12.
Unexpectedly, data show: when carbon dioxide at first was added in the calcium carbonate that will be added into subsequently in the pulp liquor, zeta potential can increase, and electrical conductivity will be descended by initial pulp liquor.In fact, the present invention is not limited to carbon dioxide is added in the composition that comprises paper pulp or paper pulp fiber fines.But can when being adjusted, the electrical property of the calcium carbonate in the composition that subsequently introducing is contained paper pulp or paper pulp fiber fines add carbon dioxide.
Table 12: with carbon dioxide is added in the calcium carbonate before pulp liquor mixes
| Sample | CO 2Volume | Temperature | pH | Zeta potential | Electrical conductivity |
| # | (mL) | (℃) | (mV) | (mS) | |
| 1 | 0 | 22.5 | 9.20 | -106.0 | 0.0456 |
| 2 | 500 | 22.5 | 9.19 | -103.1 | 0.0469 |
| 3 | 2500 | 22.5 | 8.85 | -96.7 | 0.0546 |
| 4 | 7500 | 22.5 | 8.95 | -95.9 | 0.0559 |
| 5 | 14000 | 22.5 | 8.91 | -90.5 | 0.0627 |
Carbon dioxide is to the influence of dilution plain boiled water liquid PCD
In order to investigate the influence (performance of dilution plain boiled water is referring to table 2C) of in dilution plain boiled water, adding carbon dioxide, use the glass container reactor of hollow shaft mixer (that is, hollow shaft and hollow Rushton turbine are used for gas recirculation) to carry out a series of experiments therein.The reactor that can seal has 2620 milliliters precise volumes, and is made by Verre-Labo Mula (France).Carbon dioxide adds by 1/4 pipe that is dipped in the solution (or slurries) that has sprayer.
For each experiment, 1000 gram rare (5 times of dilutions) plain boiled waters are introduced in the reactor.Should be pointed out that calcium carbonate is not added in the plain boiled water sample of dilution for these experiments.With the reactor sealing, in 1500rpm inclusions is mixed then.After reactor content was mixed 5 minutes, carbon dioxide introduced in the reactor and in 1500rpm inclusions was mixed 15 minutes.During this of short duration research, three kinds of different carbon dioxide dosage are investigated.The results are shown in Table 13.
As shown in table 13, wherein data show astoundingly: even for plain boiled water, add carbon dioxide and also can reduce the electric charge requirement effectively.
Table 13: carbon dioxide is to the PCD of dilution plain boiled water solution and the influence of electrical conductivity
| CO 2Dosage (g) | ||||
| The character of dilution plain boiled water | 0.1612g | 0.3240g | 1.6223g | |
| Temperature | 22.6℃ | 22.5℃ | 21.8℃ | 21.9℃ |
| pH | 8.18 | 6.63 | 6.38 | 5.76 |
| Electrical conductivity | 1391μS/cm | 1374μS/cm | 1364μS/cm | 1372μS/cm |
| TDS | 962.4ppm | 1005ppm | 999ppm | 1005ppm |
| PCD (10.0 mL sample) | 8.594mL?Poly- Dadmac(0.001N) | 7.578mL?Poly- Dadmac(0.001N) | 7.213mL?Poly -Dadmac(0.001N) | 6.988mL?Poly- Dadmac(0.001N) |
Carbon dioxide is to the influence of the PCD of dilution plain boiled water liquid calciferous
In order to investigate the influence (referring to the table 2C that is used to dilute plain boiled water) of in dilution plain boiled water, adding carbon dioxide, 1/4 pipe that use and have sprayer, is dipped in solution in (or slurries).
For each experiment, 990 gram dilution (5 times) plain boiled waters and 10.0 gram PCC (AlbacarHO derives from Specialty Minerals Inc.) are introduced in the reactor.With the reactor sealing, in 1500rpm inclusions is mixed then.After reactor content was mixed 5 minutes, carbon dioxide introduced in the reactor and to inclusions mixed 15 minutes.Use the plain boiled water of three kinds of different performances that added PCC (before adding carbon dioxide), use the glass container reactor of hollow shaft mixer (hollow shaft and the hollow Rushton turbine that promptly are used for gas recirculation) to experimentize therein.The reactor that can seal has 2620 milliliters precise volumes, and is made by Verre-Labo Mula (France).During this of short duration research, investigate by the carbon dioxide that different dosage adds.The results are shown in Table 14.
As shown in table 14, data show astoundingly, carbon dioxide are added into will obviously raise electrical conductivity in the plain boiled water of calcium carbonate-reinforcement and reduce PCD.Compare with the calcium fortified plain boiled water of nothing-carbonic acid, add carbon dioxide and will make the more substantial reduction of PCD.
Table 14: carbon dioxide is to the PCD with calcium carbonate (PCC) " reinforcement " dilution plain boiled water, the influence of electrical conductivity
| CO 2Dosage (g) | ||||
| The character of dilution plain boiled water (contains CaCO 3) | 0.1621g | 0.3188g | 1.6197g | |
| Temperature | 20.8℃ * | 22.3℃ | 22.6℃ | 22.5℃ |
| pH | 8.77 | 7.57 | 7.28 | 6.70 |
| Electrical conductivity | 1356μS/cm | 1561μS/cm | 1708μS/cm | 2106μS/cm |
| TDS | 994.9ppm | 1157ppm | 1264ppm | 1598ppm |
| PCD (10.0 mL sample) | 6.791mL?Poly- Dadmac(0.001N) | 5.104mL?Poly- Dadmac(0.001N) | 4.874mL?Poly -Dadmac(0.001N) | 3.060mL?Poly- Dadmac(0.001N) |
The influence of carbon dioxide is compared with the influence of sulfuric acid:
Utilize hollow shaft reactor (previously described) to carry out these experiments.In these experiments, carbon dioxide is added in the dilution plain boiled water of 1000 grams, and mixed 10 minutes in 1500rpm (utilizing the hollow shaft structure).Record pH, temperature, electrical conductivity, TDS, and PCD.Then, from reactor, take out 10.0 gram plain boiled waters, and add 10.0 gram PCC.Plain boiled water/PCC mixture that pH is adjusted mixed 10 minutes, then with regard to pH, and temperature, electrical conductivity, TDS and PCD analyze sample.List this brief research.In this table, illustrated: need the sulfuric acid of 0.573 gram, 4.0 equivalents that pH is transferred to 6.39.Carry out identical experiment, different is to substitute carbon dioxide with sulfuric acid.In other words, reach and add the identical target pH (being pH=6.39) of carbon dioxide acquisition with sulfuric acid.The results are shown in Table 17.
The result shows: when utilizing carbon dioxide and sulfuric acid recently to reach identical target pH value mutually, and the PCD the when PCD of sample is lower than use sulfuric acid slightly.After adding PCC, wherein carry out the sample of initial pH regulator and compare with the sample that carries out pH regulator with sulfuric acid and have much lower PCD with carbon dioxide.
The sulfuric acid that is used for these experiments is provided with the concentration of 4N by Fisher Scientific certified ACS.
As data listed in the table 15, compare to reach identical pH with adding sulfuric acid, add carbon dioxide electrical conductivity will be increased much morely.In addition, compare to reach identical pH, add carbon dioxide electrical conductivity will be increased much morely with adding sulfuric acid.In addition, compare to reach identical pH, add carbon dioxide the electric charge requirement will be descended much morely with adding sulfuric acid.
Table 15:pH changes the effect of agent.
| Temperature (℃) | Electrical conductivity (μ S/cm) | TDS(ppm) | pH | PCD(mL) | |
| Benchmark | 22.6 | 1391 | 962.4 | 8.18 | 8.594 |
| CO 2(0.3228g?CO 2) | 20.8 | 1388 | 1020 | 6.39 | 7.848 |
| PCC (adding 10.0g PCC) | 20.9 | 1503 | 1113 | 7.97 | 5.007 |
| H 2SO 4(0.573g?4N) | 21.5 | 1504 | 1114 | 6.39 | 7.491 |
| PCC (adding 10.0g PCC) | 21.8 | 1541 | 1142 | 8.67 | 6.097 |
Carbon dioxide is to zeta potential of " dirty " pulp liquor and the influence of PCD
Carry out this experiment,, will produce what degree modification zeta potential and PCD so that determine carbon dioxide is introduced in what is called calciferous " dirty " pulp liquor.The paper pulp that is used for preparing two kinds of slurries is: the chemical pulping that is obtained by the source that can't differentiate that is positioned at British Columbia and the hardwood pulp (HW) and the softwood pulp (SW) of bleaching, and EconotechService (Derwent, B.C., Canada) preparation.Used paper pulp comprises northern hardwood pulp, i.e. poplar slurry and northern softwood pulp.Utilization is made with extra care buying market pulp board based on the Valley beater of tappi test method no (T200sp-96).Respectively hardwood pulp and softwood pulp are refined into 461 and 451 Canadian Standard Freeness (CSF).
The concentration of the pulp liquor of Shi Yonging is 2.5% (Cy) in this experiment.Utilize the ratio of 80%HW and 20%SW to prepare pulp liquor.Utilize 10 times of dilutions (derive from and be seated in Beaupre, Quebec, Canada[Abitibi-Consolidated] pulp mill) preparation pulp liquor of previously mentioned plain boiled water.In addition, should be pointed out that the blender that is used for preparing slurries is " Square D " blender that derives from IEC Controls.
At first, with 10 times of plain boiled water dilutions, i.e. 10 times dilution.Then, utilize the 80/20HW/SW that is mixed with dilution plain boiled water, the pulp liquor of preparation 2.5%Cy.1300 gram pulp liquors are added in the reactor, and mixed 30 minutes in 1500rpm.Carry out reference measurement then.Add 13.93 gram PCC then, and mixed 15 minutes.
Measure and the record zeta potential pH, temperature, electrical conductivity, TDS, and PCD.Get 25 milliliters of samples (filtering) in addition so that carry out the PCD test by 200 orders.Interpolation is equivalent to the carbon dioxide dosage of 10 kg/ton fibers and mixed 15 minutes then.Measure and write down zeta potential then, pH, temperature, electrical conductivity, TDS, and PCD.
Use the glass container reactor of hollow shaft blender (hollow shaft and the hollow Rushton turbine that promptly are used for gas recirculation) to carry out this experiment therein.Reactor has 2620 milliliters precise volumes, and is made by Verre-Labo Mula (France).For this experiment, sealed reactor between carbon dioxide conveying and mixing period subsequently.Data shown in table 16 are such, carbon dioxide added to be similar to will make the reduction of electric charge requirement in the slurries of finding in the paper-making process and zeta potential is increased.
Table 16: carbon dioxide is to the zeta potential of " dirty " paper pulp sample, the influence of electrical conductivity and electric charge requirement
| Temperature (℃) | Electrical conductivity (μ S/cm) | TDS (ppm) | pH | Zeta potential (mV) | PCD (mL) | |
| Ww/ running | 23.4 | 878.4 | 629.2 | 8.20 | na | 2.835 |
| | 22.3 | 824.7 | 590 | 7.12 | -26.2 | 2.824 |
| PCC?30％(13.93g) | 22.3 | 861.2 | 617.5 | 8.50 | -32.3 | 1.791 |
| CO2(10kg/ton) | 22.4 | 1065.0 | 772.4 | 7.46 | -20.7 | 1.033 |
As mentioned above, data show unexpectedly: comprise paper pulp, the slurries of calcium carbonate and plain boiled water have the electrical conductivity of obvious adjustment, the electrical property of zeta potential and electric charge requirement.Particularly, reduce electric charge requirement and zeta potential, increased electrical conductivity in surprising mode simultaneously.
Shown in the embodiment of front, carbon dioxide introduced the electrical property of constituent will be adjusted, and therefore those components of paper making compositions are adjusted.This will bring many benefits to papermaker.At first, add carbon dioxide not can along with the time cause gathering in the past, and paper-making process is stopped with undesirable number of times.Secondly, the interpolation carbon dioxide will reduce, even may eliminate the demand to expensive additive, and described additive is unknown for the reliability of extend of hope.Moreover, add carbon dioxide and can carry out, as when the pulp preparation, in each position of short circuit with in the calcium carbonate serosity before being introduced in the pulp liquor in the many different position of paper-making process.
Those skilled in the art will be appreciated that scope of the present invention is not limited to above-mentioned embodiment that has or embodiment.
Claims (27)
1. method of modifying to electrical properties of papermaking compositions, described method comprises the steps: to provide at least a paper making compositions, described composition comprises gel phase, water and paper pulp fiber, and each of the gel phase of one of wherein said at least a paper making compositions, water and paper pulp fiber all has electrical property and based on the corresponding value of described electrical property; Carbon dioxide is introduced in described at least a paper making compositions at least a, and its consumption is adjusted at least 1% with corresponding electrical property value; Selection is based on the predetermined value or the predetermined range of electrical property; Measure at least a electrical property of gel phase, water and the paper pulp fiber of at least a paper making compositions, obtain a measured value thus; Measured value and predetermined value or predetermined range are compared; Selection wherein, is compared with measured value based on the carbon dioxide addition of described contrast step, and adjusted value more approaches predetermined value or predetermined range.
2. the process of claim 1 wherein: described at least a paper making compositions also comprises solid carbonic acid calcium in addition; At least a portion of solid carbonic acid calcium is dissolved when introducing the described step of carbon dioxide.
3. the method for claim 1, also comprise the steps: in addition first, second and the 3rd paper making compositions are elected to be described at least a paper making compositions, wherein: first paper making compositions is a pulp liquor, second paper making compositions is a waste paper, and the 3rd paper making compositions is the plain boiled water that does not comprise a large amount of paper pulp fibers; In the downstream of container, on papermaking wire-cloth, make the paper pulp fiber dehydration of first paper making compositions, and on papermaking wire-cloth, produce the second and the 3rd paper making compositions.
4. the method for claim 3 also comprises following steps: first paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide in addition.
5. the method for claim 3 also comprises the steps: second paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide in addition.
6. the method for claim 3 also comprises the steps: the 3rd paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide in addition.
7. the method for claim 3 also comprises: the dilution of first paper making compositions is obtained the 4th paper making compositions thus in addition; Described the 4th paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
8. the method for claim 3, wherein: corresponding electrical property value is based on zeta potential.
9. the method for claim 3, wherein: corresponding electrical property value is based on electrical conductivity.
10. the method for claim 3, wherein: corresponding electrical property value is based on the electric charge requirement.
11. the method for claim 3, wherein: corresponding electrical property value is based on streaming potential.
12. the method for claim 8, wherein: the corresponding zeta potential value of at least a gel phase of first, second and the 3rd paper making compositions is a negative value, and its adjustment to make it the negative value absolute value littler.
13. the method for claim 8, wherein: at least a gel phase of first, second and the 3rd paper making compositions and at least a corresponding zeta potential value of paper pulp fiber be on the occasion of, and its adjustment makes it on the occasion of littler.
14. the method for claim 9, wherein: first, second and at least a gel phase of the 3rd paper making compositions and at least a corresponding conductivity value of paper pulp fiber increase by adjustment.
15. the method for claim 10, wherein: at least a gel phase of first, second and the 3rd paper making compositions and at least a corresponding charge of paper pulp fiber need value to pass through to adjust to reduce.
16. the process of claim 1 wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
17. the method for claim 8, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
18. the process of claim 1 wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
19. the method for claim 14, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
20. the method for claim 15, wherein: comprise the paper pulp fiber that exists with at least 3% concentration to the described at least a paper making compositions of wherein introducing carbon dioxide.
21. the method for claim 1 also comprises the steps: to utilize adjusting device to control the amount of carbon dioxide of being introduced in addition, this adjusting device is finished described contrast step.
22. the method for claim 21, wherein, adjusting device comprises programmable logic controller (PLC).
23. the method for claim 3 also comprises the steps: the dilution of first paper making compositions is obtained the 4th paper making compositions thus in addition; Be provided for supplying the paper pulp pond of first paper making compositions; Provide receive the 4th paper making compositions and on across the papermaking wire-cloth upper surface flow box of dispense paper pulp fibres, described flow box is positioned at the downstream in paper pulp pond; With the position of select introducing carbon dioxide, this chosen position is in paper pulp Chi Chu or its downstream, and in the non-conterminous upstream of flow box.
24. the method for claim 3 also comprises the steps: to select zeta potential as electrical property in addition; First paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide; The fibre concentration of first paper making compositions is chosen as at least 3%.
25. the method for claim 3 also comprises the steps: the dilution of first paper making compositions is obtained the 4th paper making compositions thus in addition; Select zeta potential as electrical property; With the 4th paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
26. the method for claim 3 also comprises the steps: to select zeta potential as electrical property in addition; Second paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
27. the method for claim 3 also comprises the steps: to select zeta potential as electrical property in addition; The 3rd paper making compositions is elected to be to the described at least a paper making compositions of wherein introducing carbon dioxide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41487602P | 2002-09-30 | 2002-09-30 | |
| US60/414,876 | 2002-09-30 | ||
| US10/656,857 | 2003-09-06 | ||
| US10/656,857 US7056419B2 (en) | 2002-09-30 | 2003-09-06 | Methods for modifying electrical properties of papermaking compositions using carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1685110A CN1685110A (en) | 2005-10-19 |
| CN100342082C true CN100342082C (en) | 2007-10-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038233169A Expired - Fee Related CN100342082C (en) | 2002-09-30 | 2003-09-17 | Method for Improving Electrical Properties of Papermaking Compositions Using Carbon Dioxide |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7056419B2 (en) |
| EP (1) | EP1552059A1 (en) |
| JP (1) | JP4448089B2 (en) |
| CN (1) | CN100342082C (en) |
| AU (1) | AU2003263428A1 (en) |
| BR (1) | BR0313820A (en) |
| CA (1) | CA2495006C (en) |
| WO (1) | WO2004029359A1 (en) |
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| US20040256069A1 (en) * | 2003-06-18 | 2004-12-23 | Saucedo Victor M. | Estimation and control in the wet end using CO2 |
| EP1955063A1 (en) * | 2005-11-28 | 2008-08-13 | BTG Instruments GmbH | Device for analysing sample fluids containing suspended materials |
| JP4801478B2 (en) * | 2006-03-27 | 2011-10-26 | 日本製紙株式会社 | How to treat broke pulp |
| EP2199462A1 (en) * | 2008-12-18 | 2010-06-23 | Coöperatie Avebe U.A. | A process for making paper |
| FI122304B (en) | 2010-04-22 | 2011-11-30 | Nordkalk Oy Ab | Use of acidic water in paper making |
| US9643894B2 (en) * | 2012-06-18 | 2017-05-09 | Toyota Motor Engineering & Manufacturing North America, Inc. | High surface area carbon opals and inverse opals obtained therefrom |
| CA2881426C (en) * | 2012-08-10 | 2020-07-21 | International Paper Company | Fluff pulp and high sap loaded core |
| CN103726396B (en) * | 2013-12-18 | 2016-08-17 | 安徽华邦特种材料有限公司 | A kind of production method of high-stiffness thermal transfer body paper |
| US10519607B2 (en) | 2016-05-23 | 2019-12-31 | Gpcp Ip Holdings Llc | Dissolved air de-bonding of a tissue sheet |
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- 2003-09-17 WO PCT/IB2003/003997 patent/WO2004029359A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2004029359A1 (en) | 2004-04-08 |
| JP2006501383A (en) | 2006-01-12 |
| CA2495006A1 (en) | 2004-04-08 |
| US7056419B2 (en) | 2006-06-06 |
| US20040118539A1 (en) | 2004-06-24 |
| CA2495006C (en) | 2008-04-08 |
| JP4448089B2 (en) | 2010-04-07 |
| AU2003263428A1 (en) | 2004-04-19 |
| CN1685110A (en) | 2005-10-19 |
| EP1552059A1 (en) | 2005-07-13 |
| BR0313820A (en) | 2005-07-05 |
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